Abstract
Photoresponsive polypeptides, poly(l-glutamic acid) containing 1.9, 14.1, 46.3 mol% azobenzenesulfonate moieties in the side chains (azo·S-PGA), have been prepared by the condensation reaction of poly(l-glutamic acid) (PGA, Mv=1.19×105) with 4-amino-1,1′-azobenzene-4′-sulfonic acid sodium salt in dimethylformamide (DMF) solution and the membranes were obtained by casting their DMF solution with 4,4′-diaminodiphenylmethane as a cross-linking agent. trans to cis Isomerization of the azobenzenesulfonate moieties induced by ultraviolet (UV) light resulted in α-helix to coil transition in the membrane composed of azo·S-PGA containing 14.1 mol% azobenzenesulfonate moieties at adequate pHs, indicating the electrostatic repulsion between the sulfonate anions in the azo photochromic side chains and the neighboring glutamate anions to be enhanced by photoinduced changes in the geometry of the azo chromophores. As a result, the membrane potentials of azo·S-PGA membrane containing 14.1 mol% azobenzenesulfonate moieties were strongly dependent on UV light irradiation. It was also found that photoinduced changes of the membrane structure and membrane potentials were irreversible. On the other hand, the structure of the azo·S-PGA membrane containing 1.9 and 46.3 mol% azobenzenesulfonate moieties was shown to be independent of UV light irradiation at any pH. The former ineffectiveness of the light irradiation was attributed to small amounts of azo photochromic moieties and the latter to the fact that the azo·S-PGA membranes with large amounts of azobenzenesulfonate moieties are in random coil structures at any pH even in the drk.
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Sato, M., Kinoshita, T., Takizawa, A. et al. Photocontrol of Polypeptide Membrane Structure and Functions by cis-trans Isomerization in Side-Chain Azobenzenesulfonate Groups. Polym J 21, 533–541 (1989). https://doi.org/10.1295/polymj.21.533
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DOI: https://doi.org/10.1295/polymj.21.533
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